US7431868B2 - Method of manufacturing a metal substrate for an oxide superconducting wire - Google Patents
Method of manufacturing a metal substrate for an oxide superconducting wire Download PDFInfo
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- US7431868B2 US7431868B2 US11/239,204 US23920405A US7431868B2 US 7431868 B2 US7431868 B2 US 7431868B2 US 23920405 A US23920405 A US 23920405A US 7431868 B2 US7431868 B2 US 7431868B2
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- 239000000758 substrate Substances 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000013078 crystal Substances 0.000 claims abstract description 44
- 238000005096 rolling process Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 95
- 230000001590 oxidative effect Effects 0.000 claims description 66
- 239000007789 gas Substances 0.000 claims description 40
- 239000002887 superconductor Substances 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005299 abrasion Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004943 liquid phase epitaxy Methods 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910021523 barium zirconate Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0576—Processes for depositing or forming copper oxide superconductor layers characterised by the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49014—Superconductor
Definitions
- the present invention relates to a metal substrate for an oxide superconducting wire, an oxide superconducting wire, and a method of manufacturing the oxide superconducting wire.
- a tape-like wire which can be obtained through a process wherein a stabilized zirconia (YSZ) is deposited on a Hastelloy tape by means of an ion beam-asisted deposition (IBAD) method, thereby controlling the crystal orientation of zirconia with c-axis thereof being oriented with the tape and a- and b-axes thereof being aligned with the tape (in-plane orientation), and a Y123(YBa 2 Cu 3 O 7 ⁇ y )-based oxide superconducting film is formed on the zirconia layer by means of a laser abrasion. Since this tape-like wire is excellent in crystal alignment of a- and b-axes thereof, the critical current density (J c ) would become as high as 0.5-1.0 ⁇ 10 6 A/cm 2 under the conditions of 77K and zero Tesla.
- J c critical current density
- the gist of this method resides in that an oxide film is formed on the surface of metal tape only through the oxidation of the surface of the metal tape and that the oxide film is utilized as an intermediate layer in the same manner as the aforementioned YSZ or CeO 2 .
- This method is suited for mass production and hence considered as a practical method.
- the enhancement of orientation of oxide crystal is not taken into consideration at all.
- the J c of oxide superconducting layer formed on this oxide film by means of sputtering method is at most 1 ⁇ 10 3 A/cm 2 or so, which is as low as about one thousandth of that of the aforementioned high orientation tape wire.
- a method of manufacturing a superconducting wire wherein a polycrystalline metal substrate is subjected to rolling work, heated at a temperature of 900° C. or more in a non-oxidizing atmosphere to obtain a rolled aggregate structure where the ⁇ 100 ⁇ plane is parallel to the rolled surface and the ⁇ 001> axis is parallel to the rolling direction (hereinafter referred to as ⁇ 100 ⁇ 001> crystal orientation), and further heated at a temperature of 1000° C.
- an oxide crystal layer consisting of an oxide of polycrystalline metal where 90% or more of the ⁇ 100 ⁇ plane is oriented so as to become parallel to the surface of the aforementioned polycrystalline metal substrate at an angle of 10° or less, and an oxide superconductor layer is deposited on this oxide crystal layer (see for example, JP Laid-open Patent Publication (Kokai) No. 11-3620 (1999)).
- the present invention has been accomplished under these circumstances and hence, the objects of the present invention are to provide a metal substrate for an oxide superconducting wire which makes it possible to form an oxide superconducting wire of high critical current density, an oxide superconducting wire exhibiting a high critical current density, and a method of manufacturing the oxide superconducting wire.
- the present invention provides a metal substrate for an oxide superconducting wire, which comprises: a polycrystalline metal substrate with a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction; and an oxide crystal layer comprising an oxide of the polycrystalline metal and formed on a surface of the polycrystalline metal substrate; wherein at least 90% of grain boundaries in the oxide crystal layer have an inclination of 10° or less; and at least 90% of the ⁇ 100 ⁇ plane of the oxide crystal layer make an angle of 10° or less with the surface of the polycrystalline metal substrate.
- the polycrystalline metal constituting the substrate may be formed of nickel or a nickel-based alloy.
- an oxide superconducting wire which comprises: a polycrystalline metal substrate with a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction; an oxide crystal layer comprising an oxide of the polycrystalline metal and formed on a surface of the polycrystalline metal substrate; and an oxide superconductor layer formed on the oxide crystal layer; wherein at least 90% of grain boundaries in the oxide crystal layer have an inclination of 10° or less; and at least 90% of the ⁇ 100 ⁇ plane of the oxide crystal layer make an angle of 10° or less with the surface of the polycrystalline metal substrate.
- At least 90% of grain boundaries in the oxide superconductor layer have an inclination which is confined to 10° or less; and at least 90% of the ⁇ 100 ⁇ plane of the oxide superconductor layer make an angle of 10° or less with the surface of the polycrystalline metal substrate.
- the oxide superconductor layer may be constituted by a crystal represented by the formula RE 1+x Ba 2 ⁇ x Cu 3 O y (wherein RE is one kind or two or more kinds of elements selected from the group consisting of Y, Nd, Sm, Gd, Eu, Yb and Pr).
- the present invention provides a metal substrate for an oxide superconducting wire, comprising: subjecting a polycrystalline metal substrate with a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction, to a first heat treatment at a low oxidizing rate in an atmosphere containing an oxidizing gas; and subjecting the polycrystalline metal substrate that has been subjected to the first heat treatment to a second heat treatment at a high oxidizing rate in an atmosphere containing an oxidizing gas to thereby form an oxide crystal layer where at least 90% of the grain boundary have an inclination of 10° or less.
- the oxidizing gas is a gas capable of exhibiting an oxidizing effect such as O 2 , H 2 O, O 3 , etc.
- the oxidizing rate of the first heat treatment may preferably be confined within the range of 0.01-0.2 ⁇ m/hr, and the oxidizing rate of the second heat treatment may preferably be confined within the range of 1-10 ⁇ m/hr.
- the first heat treatment may preferably be performed in an atmosphere containing a smaller quantity of oxidizing gas than that contained in the second heat treatment. More specifically, the temperature of heat treatment in the first heat treatment may preferably be higher than 247° C. and not higher than 1200° C., and the temperature of heat treatment in the second heat treatment may preferably be higher than 800° C. and not higher than 1300° C.
- the heat-treating atmosphere in the first heat treatment may be an atmosphere containing a minute amount of an oxidizing gas that can be created by continuously drawing a vacuum while flowing argon gas therein.
- the heat-treating atmosphere in the second heat treatment may be an atmosphere containing a large quantity of an oxidizing gas.
- the present invention provides a method of manufacturing an oxide superconducting wire, comprising: subjecting a polycrystalline metal substrate with a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction to a first heat treatment at a low oxidizing rate in an atmosphere containing a minute amount of oxidizing gas; subjecting the polycrystalline metal substrate that has been subjected to the first heat treatment to a second heat treatment at a high oxidizing rate in an atmosphere containing a large quantity of oxidizing gas to thereby form an oxide crystal layer where at least 90% of grain boundary have the inclination of 10° or less; and forming an oxide superconductor layer on a surface of the oxide crystal layer.
- the oxide superconductor layer may preferably be formed by means of laser abrasion or by means of liquid phase epitaxy.
- an oxide superconducting wire In the method of manufacturing an oxide superconducting wire according to the present invention as described above, since an oxide crystal layer which is excellent in orientation, i.e. at least 90% of inclination of grain boundary is confined to 10° or less, is already formed on a surface of the polycrystalline metal substrate as described above, the oxide superconductor layer to be formed thereon is also excellent in orientation. As a result, it is possible to obtain an oxide superconducting wire exhibiting a high critical current density.
- FIG. 1A is a pole figure of the oxide crystal layer obtained in Example 1;
- FIG. 1B is a graph showing a pattern of angle distribution of the oxide crystal layer obtained in Example 1;
- FIG. 2A is a pole figure of the oxide crystal layer obtained in Comparative Example
- FIG. 2B is a graph showing a pattern of angle distribution of the oxide crystal layer obtained in Comparative Example
- FIG. 3A is a pole figure of the oxide superconductor layer obtained in Example 3.
- FIG. 3B is a graph showing a pattern of angle distribution of the oxide superconductor layer obtained in Example 3.
- the metal substrate for an oxide superconducting wire according to a first aspect of the present invention is characterized in that an oxide crystal layer exhibiting excellent in-plane orientation, i.e. at least 90% of grain boundaries thereof have an inclination which is confined to 10° or less, and also exhibiting excellent out-of-plane orientation, i.e. at least 90% of the ⁇ 100 ⁇ plane thereof make an angle of 10° or less with the surface of the polycrystalline metal substrate, is formed on the surface of the polycrystalline metal substrate.
- This kind of oxide crystal layer can be formed by subjecting the surface of polycrystalline metal substrate to two-stage oxidizing treatments in an atmosphere containing an oxidizing gas.
- the oxidizing gas useful in the present invention it is possible to employ O 2 , H 2 O, O 3 , etc.
- the polycrystalline metal substrate is required to have a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction. Unless the polycrystalline metal substrate is provided with this rolled aggregate structure, it would be impossible to form an excellent oxide crystal layer and an oxide superconductor layer both excellent in orientation on the surface of the polycrystalline metal substrate.
- a polycrystalline metal substrate having such a rolled aggregate structure can be obtained, for example, through rolling work and heat treatment in a non-oxidizing atmosphere.
- nickel or nickel-based alloys As for the materials for polycrystalline metal substrate, it is preferable to employ nickel or nickel-based alloys. As for the nickel-based alloys, it is possible to employ nickel-chromium, nickel-vanadium, nickel-silicon, nickel-aluminum, nickel-zinc, nickel-copper, etc.
- the two-stage oxidizing treatments in an atmosphere containing an oxidizing gas is consisted of a first heat treatment where the oxidizing rate is relatively low, and a second heat treatment where the oxidizing rate is relatively high.
- the oxidizing rate in the first heat treatment may preferably be confined within the range of 0.01-0.2 ⁇ m/hr, and the oxidizing rate in the second heat treatment may preferably be confined within the range of 1-10 ⁇ m/hr.
- the oxidizing rate in the first heat treatment is faster than 0.2 ⁇ m/hr, it would become difficult to obtain an oxide crystal layer which is excellent in orientation.
- the oxidizing rate in the first heat treatment is lower than 0.01 ⁇ m/hr, it would take too long time in obtaining a prescribed film thickness, thus raising a problem that the working efficiency would be deteriorated.
- the oxidizing rate in the second heat treatment is faster than 10 ⁇ m/hr, it would become difficult to obtain an oxide crystal layer which is excellent in orientation.
- the oxidizing rate in the second heat treatment is lower than 1 ⁇ m/hr, it would take too long time in obtaining a prescribed film thickness, thus raising a problem that the working efficiency would be deteriorated.
- the first heat treatment may preferably be performed in an atmosphere containing a smaller quantity of oxidizing gas than that contained in the second heat treatment. More specifically, the temperature of heat treatment in the first heat treatment may be higher than 247° C. and not higher than 1200° C., and the temperature of heat treatment in the second heat treatment may be higher than 800° C. and not higher than 1300° C.
- the temperature of heat treatment in the first heat treatment is not higher than 247° C., it would be practically impossible to obtain an oxide crystal.
- the temperature of heat treatment in the first heat treatment is higher than 1200° C., the oxidizing rate would become too fast so that it would be difficult to obtain an oxide crystal layer excellent in orientation.
- the temperature of heat treatment in the second heat treatment is not higher than 800° C., the oxidizing rate would become too slow, thereby raising problem of working efficiency. If the temperature of heat treatment in the second heat treatment is higher than 1300° C., it would be difficult to obtain an oxide crystal layer excellent in orientation.
- the atmosphere in the first heat treatment may preferably be an atmosphere containing a minute quantity of oxidizing gas. This kind of atmosphere can be created by continuously drawing a vacuum while flowing argon gas therein until an atmosphere containing a minute quantity of oxidizing gas can be obtained.
- the heat-treating atmosphere in the second heat treatment is an atmosphere containing a larger quantity of an oxidizing gas than that of the atmosphere in the first heat treatment. This atmosphere containing a larger quantity of an oxidizing gas may be air atmosphere.
- the partial pressure of the oxidizing gas in the atmosphere in the first heat treatment may preferably be 10 ⁇ 5 atm or less if oxygen is employed as the oxidizing gas, and the partial pressure of the oxygen gas in the atmosphere in the second heat treatment may preferably be 0.2 atm or more.
- a metal substrate for an oxide superconducting wire wherein an oxide crystal layer exhibiting excellent in-plane orientation, i.e., at least 90% of grain boundaries thereof have an inclination which is confined to 10° or less, and also exhibiting excellent out-of-plane orientation, i.e. at least 90% of the ⁇ 100 ⁇ plane thereof make an angle of 10° or less with the surface of the polycrystalline metal substrate, is formed on the surface of the polycrystalline metal substrate.
- the oxide superconducting wire according to the second aspect of the present invention is featured in that an oxide superconductor layer is formed on the surface of the metal substrate for an oxide superconducting wire to be obtained according to the first aspect of the present invention.
- the oxide superconductor layer to be formed on the oxide film is enabled to exhibit an excellent orientation, i.e. at least 90% of grain boundaries thereof is confined to 10° or less and at least 90% of the ⁇ 100 ⁇ plane thereof make an angle of 10° or less with the surface of the polycrystalline metal substrate.
- the oxide superconductor layer it is possible to employ an ordinary superconductor, e.g. a superconductor represented by the formula RE 1+x Ba 2 ⁇ x Cu 3 O y (wherein RE is one kind or two or more kinds of elements selected from the group consisting of Y, Nd, Sm, Gd, Eu, Yb and Pr).
- RE is one kind or two or more kinds of elements selected from the group consisting of Y, Nd, Sm, Gd, Eu, Yb and Pr).
- a diffusion barrier layer may be formed on the surface of oxide crystalline layer prior to the step of forming the oxide superconductor layer.
- the diffusion barrier layer it is possible to employ BaZrO 3 , CeO 2 , Y 2 O 3 , etc.
- the formation of the oxide superconductor layer can be performed by means of laser abrasion or by means of liquid phase epitaxial method.
- the laser abrasion it is required, in order to create a film of high quality, to keep the substrate at a high temperature, i.e. about 700-800° C.
- the liquid phase epitaxial method which makes it possible to perform a high-speed film-forming, since the substrate is immersed in a high-temperature melt of 900-1000° C., it would be difficult to deposit the oxide superconductor layer directly on a metal substrate of low melting point.
- nickel or nickel-based alloys both high in melting point, are employed as a polycrystalline metal substrate, it is possible to deposit an oxide superconductor layer by means of laser abrasion or liquid phase epitaxial method.
- an oxide film excellent in orientation i.e., at least 90% of grain boundaries thereof have an inclination which is confined to 10° or less and at least 90% of the ⁇ 100 ⁇ plane thereof make an angle of 10° or less with the surface of the polycrystalline metal substrate, is formed in advance on the surface of substrate, it is possible to form, through this oxide film, an oxide superconductor layer excellent in orientation on the surface of substrate. As a result, it is possible to obtain an oxide superconducting wire which is high in critical current density.
- a polycrystalline nickel substrate having a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction was prepared.
- This substrate was placed in a heating furnace and subjected to a first heat treatment for 20 hours at a temperature of 750° C. and in an atmosphere containing a minute quantity of oxidizing gas created by continuously evacuating the heating furnace while introducing argon gas therein.
- an average film-forming speed of this first heat treatment was measured, it was 0.15 ⁇ m/hr.
- the polycrystalline nickel substrate having a thin NiO film formed thereon by the first heat treatment was further subjected to a second heat treatment in a heating furnace for one hour at a temperature of 1000° C. and in air atmosphere to form an NiO film having a thickness of 4 ⁇ m.
- a second heat treatment in a heating furnace for one hour at a temperature of 1000° C. and in air atmosphere to form an NiO film having a thickness of 4 ⁇ m.
- an average film-forming speed of this second heat treatment was measured, it was 1 ⁇ m/hr.
- the inclination of grain boundary of the NiO film was measured.
- the inclination of grain boundary was determined as follows. Namely, a pole figure of the NiO film was prepared by means of X-ray diffraction and then, by scanning this pole figure, an X-ray diffraction pattern was obtained. Then, a half band width ⁇ was determined from the X-ray diffraction pattern, thus obtaining the inclination of grain boundary.
- FIGS. 1A and 1B The results are shown in FIGS. 1A and 1B .
- FIG. 1A shows the pole figure
- FIG. 1B shows a pattern of angle ( ⁇ ) distribution ( ⁇ corresponds to the angle of rotation of the sample) which was obtained through the scanning, in counterclockwise, of the pole figure of FIG. 1A .
- ⁇ angle
- the NiO layer formed in this example was formed of a crystal exhibiting a high degree of orientation in-plane.
- a polycrystalline nickel substrate having a rolled aggregate structure having a ⁇ 100 ⁇ plane which is parallel to the rolled surface and a ⁇ 001> axis which is parallel to the rolling direction was prepared. This substrate was placed in a heating furnace and subjected to a first heat treatment for one hour at a temperature of 1100° C. and in an atmosphere containing a minute quantity of oxidizing gas created by continuously evacuating the heating furnace while introducing argon gas therein.
- the polycrystalline nickel substrate having a thin NiO film formed thereon by the first heat treatment was further subjected to a second heat treatment in a heating furnace for two hours at a temperature of 1200° C. and in air atmosphere to form an NiO film having a thickness of 6 ⁇ m.
- a second heat treatment in a heating furnace for two hours at a temperature of 1200° C. and in air atmosphere to form an NiO film having a thickness of 6 ⁇ m.
- the average film-forming speed of this second heat treatment was measured, it was 6 ⁇ m/hr.
- the inclination of grain boundary of the NiO film was measured.
- the inclination of grain boundary was determined as follows. Namely, a pole figure of the NiO film was prepared by means of X-ray diffraction and then, by scanning this pole figure, an X-ray diffraction pattern was obtained. Then, a half band width ⁇ was determined from the X-ray diffraction pattern, thus obtaining the inclination of grain boundary.
- Example 2 By making use of the same polycrystalline nickel substrate as employed in Example 1 was subjected to heat treatment in the same manner as conventionally performed, i.e., for one hour at a temperature of 1000° C. and in air atmosphere to form a NiO film. When the average film-forming speed of this heat treatment was measured, it was 5 ⁇ m/hr.
- FIGS. 2A and 2B show the pole figure of the NiO film and a pattern of angle distribution of the NiO film, respectively. It will be seen from FIGS. 2A and 2B that in this comparative example, since the surface of substrate was rapidly oxidized in a high oxidizing gas atmosphere, the half band width ⁇ thereof was 12.9°, which was much higher than that of Example 1, thus deteriorating the in-plane orientation thereof.
- the surface of the substrate obtained in Example 1 was buffed to obtain a polished surface on which a BaZrO 3 film was formed as a diffusion barrier layer by means of laser abrasion using KrF excimer laser.
- the deposition of the BaZrO 3 film was performed in an Ar gas atmosphere of 20 mm Torr in pressure with the repeating frequency of laser being set to the range of 10-20 Hz and the temperature of the substrate being controlled to 600-700° C.
- a Y123 oxide superconductor layer was formed by means of laser abrasion.
- the deposition of the Y123 oxide superconductor layer was performed in an O 2 gas atmosphere of 100-200 mm Torr in pressure with the repeating frequency of laser being set to the range of 10-20 Hz and the temperature of the substrate being controlled to 700-800° C.
- Y123 oxide superconductor layer was further deposited a Y—Yb123 oxide superconductor layer by means of liquid phase epitaxy. More specifically, powder of Yb 2 BaCuO 3 was placed at the bottom portion of crucible and then a mixture of 3BaCuO 2 +5CuO was placed over the powder. The resultant crucible made of Y 2 O 3 was heated in an electric furnace to melt these materials placed therein. The surface of the resultant melt was kept at a temperature of 950°-970° C. and then a sample was immersed in the melt to form a Y—Yb123 oxide superconductor layer.
- the present invention it is possible to provide a metal substrate for an oxide superconducting wire having an oxide crystal layer formed on the surface thereof and exhibiting excellent in-plane orientation and out-of-plane orientation which the prior art failed to achieve. Further, since it is designed such that an oxide superconductor layer is deposited on this metal substrate for an oxide superconducting wire, it is possible to obtain an oxide superconductor excellent in orientation, thus making it possible to obtain an oxide superconducting wire of high critical current density.
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Application Number | Priority Date | Filing Date | Title |
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JP2003094792 | 2003-03-31 | ||
JP2003-094792 | 2003-03-31 | ||
PCT/JP2004/004587 WO2004088677A1 (en) | 2003-03-31 | 2004-03-31 | Metal base plate for oxide superconductive wire rod, oxide superconductive wire rod and process for producing the same |
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PCT/JP2004/000458 Continuation WO2004068757A1 (en) | 2003-01-31 | 2004-01-21 | Ofdm signal collision position detection device and ofdm reception device |
PCT/JP2004/004587 Continuation WO2004088677A1 (en) | 2003-03-31 | 2004-03-31 | Metal base plate for oxide superconductive wire rod, oxide superconductive wire rod and process for producing the same |
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US20060019832A1 US20060019832A1 (en) | 2006-01-26 |
US7431868B2 true US7431868B2 (en) | 2008-10-07 |
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EP (1) | EP1640999A4 (en) |
JP (1) | JP4694965B2 (en) |
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US20080210909A1 (en) * | 2006-12-28 | 2008-09-04 | Che-Hsiung Hsu | Compositions of polyaniline made with perfuoropolymeric acid which are heat-enhanced and electronic devices made therewith |
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Also Published As
Publication number | Publication date |
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EP1640999A1 (en) | 2006-03-29 |
CN1777963A (en) | 2006-05-24 |
EP1640999A4 (en) | 2010-01-27 |
US20060019832A1 (en) | 2006-01-26 |
CN100365741C (en) | 2008-01-30 |
KR20050118294A (en) | 2005-12-16 |
WO2004088677A1 (en) | 2004-10-14 |
JPWO2004088677A1 (en) | 2006-07-06 |
JP4694965B2 (en) | 2011-06-08 |
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